Azodyestuffs containing chromium and process of making same



Patented June 15, 1926.

UNITED STATES PATENT OFFICE.

MAXISLEB AND LUCAS VON MECHEL, OF BASEL, SWITZERLAND, ASSIGNORS TO CIETYOF C HEMICAL INDUSTRY IN BASLE, OF BASEL, SWITZERLAND.

AZODYESTUFFS CONTAINING GI-IROMIUM AND PROCESS OF MAKING SAME.

No Drawing. Original application filed December 9, 1924, Serial No. 754,841, and in Switzerland Zoecamber 28, 1923. Divided and this application filed December 1, 19%. Serial No. 72,581.

The present application, which is a division of our application Serial No. 7 54,841, .filed December 9th, 1924, relates to new azo dyestuffs containing chromium. It comprises the new dyestuffs, the process of makin same, as well as the material dyed with t e new dyestuffs.

It has been found that new azo dyestuffs containing chromium may be obtained b treating the dyestufi's corresponding wit the general formula:

H00 OOH wherein R stands for any aromatic residue, which dyestufi's are obtainable as described in the application Serial No. 7 54,84E1, filed December 9th, 1924: by coupling diazo compounds with 3-hydroxynaphthalene-1.8-dicarboxylic acid, with agents yielding metals, such as compounds of copper and especially of chromium. These new dyestufi's are derivatives of the az'o dyestuffs corresponding to the general formula mentioned above. They form blackish powders, dissolving in water and in caustic soda solution with violet and blue coloration, and yielding, when printed on cotton with chromium mordants, from Bordeaux red to violet, ey and black tints which are fast, and w ich dyestufi's, when treated with reducin'g agents, split into anaromatic amino compound and the 4-amin'o-3-hydroxynaphthalene-1:8-dicarboxylic acid.

- The following examples illustrate the invention without limiting it, the parts being by weight I Example 1. A paste of hydrated chromium oxide containing .40 parts of water and corresponding with 8.5 parts of Or O 24 parts of potassium hydroxide, and 9 parts of glycerin are heated together until a complete solution is formed. The latter is diluted to 150 parts, then mixed with 22 parts of the dyestufl from diazotized 4-chloro-2-amino-l-phenol and 3-hydroxynaphthalene-1: S-dicarboxylic acid corresponding most probably with the formula:

and the whole boiled in a reflux apparatus filtered and dried. It forms a blackish Ewample 2. 52.7 parts of the dyestufi obtainable by coupling the nitrated diazo compound of the 1-amino-2 hydroxynaphthalene 4- sulfonic acid with the 3-hydroxynaphthalene-1:8-di carboxylic acid corresponding most probably with the formula: p

soil:

H0O 00H are dissolved in 1000 parts of hot water. The solution is mixed with an aqueous solution of chromium formate corresponding with 22.8 parts of 0130 and is boiled in a reflux apparatus until no in the solution is observable. The chromium dyestufi. thus formed is salted out, filtered and dried. It is a blackish powder, soluble in water, to a black-blue solution which passes to dark-violet on addition of caustiosoda solution; in concentrated sulphric: acid it dissolves to a blue-green solution.

In an acid bath it dyes wool dark green tints; on cotton it prints fast {grey tints.

The azo dyestufi containing chromium obtained from diazotized EZ-amino-l-phenoli-sulfo-G-carboxylic acid, when printed on cotton, yields Bordeaux tints; the dyestufi containing chromium from diazotized 4:6- dinitro-2-amino-1-phenol reddish-grey tints and the dyestufi' containing chromium from diazotized 5-nitro-2 'amino-l-phenol blackish tints.

at we claim is 1. As a new process the herein described manufacture of new azo ing chromi which are derivatives of the dyestufi's corresponding to the general formula:

H00 OOH l wherein R standsfor any aromatic residue,

.manufacture 0 mg chromium which are derivatives of the.

new azo dyestuifs containdyestufls corresponding to the general formula:

wherein R stands for any aromatic residue having a hydroxyl group in ortho-position to the azobridge,consist1ng in treating the dyestuffs obtainable by coupling 3-hydroxynaphthalene-1;S-dicarboxylic acid with adiazotized aromatic ortho-hydroxy amino compound, with agents adapted to yield chromium.

3. Asa new process the herein described manufacture of new azo dyestufii's containing further change of color dyestufis containare capable of being split into an aromatic chromium which are derivatives of the dyestuffs corresponding to the general formula:

N==NR- noo wherein lit stands for any aromatic residue, which dyestufis form blackish powders, dis solving in water and in caustic soda solution to violet and blue solutions, yielding, when printed on cotton with chromium mordants, fast Bordeaux -to violet, grey and black tints, and which dyestufis are capable of be- L ing split into an aromatic amino compound and 4c-amino-3-hydroxynaphthalene-1 8-dicarboxylic acid on treatment with reducing agents 5. As new products the herein described new azo dyestufi's containing chromium, which are derivatives of the dyestufis corresponding to the general formula:

wherein R stands for any aromatic residue having a hydroxyl group in ortho-position to the azobi'idge, which dyestufl's form blackish powders, dissolving in water and inp caustic soda solution to violet and blue solutions, yielding, when printed on cotton with chromium mordants, fast Bordeaux to violet and grey tints, and which dyestuffs 12B ortho-hydroxyamino compound and 4-a mino- 3-hydroxynaphthalene-1 8-dicarboxylic acid on treatment with reducing agents.

6. As new products the herein described new azo dyestuffs containing chromium, which are derivatives of the dyestuffs corre sponding to the general formula:

wherein R stands for any aromatic residue of the benzene series having a hydroxyl group in orthoosition to the azobridge, which dyestuffs orm blackish powders, dissolving in waterand in caustic soda solution to violet and blue solutions, yielding, when printed on cotton with chromium morda-nts, ast Bordeaux to violet and grey tints, and which dyestuffs are capableof being split into an ortho-aminophenol compound and 4-amino-3-hydroxynaphthalene-1 S-dicarboxylic acid on treatment with reducing agents.

7. The material dyed with thenew dyestuffs of claim 4.

8. The material dyed with the new dyestuffs of claim 5.

9. The material dyed with the new dyestuffs of claim 6.

In witness whereof we have heleunto signed our names this 21st day of November, 1925.

MAX ISLER. LUCAS VON MECHEL. 

